Dithioether-based cosmetic compositions for the treatment of the oily state of hair and skin

ABSTRACT

A cosmetic composition for the treatment of the oily appearance of hair and skin so as to reduce or eliminate said oily appearance comprises in a suitable cosmetic vehicle at least one compound of the formula ##STR1## wherein R 1  is either ##STR2## wherein r&#39; and r&#34; can be hydrogen, 2-hydroxy ethyl, 2-hydroxy propyl or 2,3-dihydroxy propyl, R 2  is --CH 3 , --CO 2  H, --C 6  H 5  P-OCH 3 , --C 6  H 5 , ##STR3## wherein R 4  is --CH 2  COOH or --COCH 3  or ##STR4## wherein R 5  is --OH, --OCH 3 , --OC 4  H 9  or --OCH 2  COOH and R 3  is hydrogen or methyl, or R 2  and R 3  together form --(CH 2 ) m  --or ##STR5## wherein m is 3-5 and n is 2-5.

The present invention relates to a new cosmetic composition for thetreatment of the oily appearance of the hair and skin.

The present invention also relates to new chemical compounds and to aprocess of producing them.

BACKGROUND OF THE INVENTION

Heretofore in an effort to combat efficiently against the oily state orappearance of the hair and skin, there have been employed compositionscontaining sulfur derivatives and, principally, thioethers derived fromcysteine or cysteamine.

GENERAL DESCRIPTION OF THE INVENTION

The present invention relates to the use of a new class of sulfurderivatives and, principally, to dithioethers which provide excellentresults in the treatment of the oily appearance of the hair and skin bysignificantly reducing or eliminating this oily and unaestheticappearance.

Thus, the present invention relates to a cosmetic composition for thetreatment of the oily appearance of the hair and skin, said compositioncontaining in combination in a suitable cosmetic vehicle or carrier, atleast one active compound of the formula: ##STR6## wherein R₁ representseither ##STR7## wherein r' and r" each independently represent hydrogen,2-hydroxy ethyl, 2-hydroxy propyl or 2,3-dihydroxy propyl,

R₂ represents a member selected from the group consisting of

(i) --CH₃,

(ii) --CO₂ H,

(iii) --C₆ H₅ p-OCH₃,

(iv) --C₆ H₅,

(v) ##STR8## (vi) ##STR9## wherein R₄ represents --CH₂ COOH or --COCH₃,and (vii) ##STR10## wherein R₅ represents --OH, --OCH₃, --OC₄ H₉ or--OCH₂ COOH, and

R₃ represents either hydrogen or methyl, or R₂ and R₃ together form adivalent radical of the formula --(CH₂)_(m) -- or ##STR11## wherein m is3-5 inclusive and n is 2-5 inclusive.

When in formula I, above, R₁ represents ##STR12## the active compoundcan be provided in the form of a salt obtained with the aid of a mineralor organic acid, such as for example, hydrochloric acid, malic acid,tartaric acid, camphosulfonic acid and the like.

Also, when in formula I, R₁ represents ##STR13## the active compoundscan be provided in the form of mono- or di-salts obtained with the aidof a mineral base such as for example an alkali or alkaline earthhydroxide (sodium, potassium and the like) or with the aid of an organicamine, such as for example triethanolamine.

Representative active compounds of formula I, useful in the compositionsof the present invention, include for instance:

(1) 2,2'-(isopropylidene dithio) diethylamine,

(2) bis-(2-amino ethylthio) acetic acid,

(3) α,α'-(p-methoxy benzylidene dithio) disuccinic acid,

(4) 2,2'-(p-methoxy benzylidene dithio) diethylamine,

(5) α,α'-(benzylidene dithio) disuccinic acid,

(6) α,α'-(piperonylidene dithio) disuccinic acid,

(7) 2,2'-(piperonylidene dithio) diethylamine,

(8) 2,2'-(2-carboxymethyloxy benzylidene dithio) diethylamine,

(9) α,α'-(vanillylidene dithio) disuccinic acid,

(10) 2,2'-(vanillylidene dithio) diethylamine,

(11) α,α'-(veratrylidene dithio) disuccinic acid,

(12) 2,2'-(veratrylidene dithio) diethylamine,

(13) α,α'-(4-butoxy-3-methoxy benzylidene dithio) disuccinic acid,

(14) 2,2'-(4-butoxy-3-methoxy benzylidene dithio) diethylamine,

(15) α,α'-(4-carboxymethyloxy-3-methoxy benzylidene dithio) disuccinicacid,

(16) 2,2'-(4-carboxymethyloxy-3-methoxy benzylidene dithio)diethylamine,

(17) 2,2'-(cyclohexylidene dithio) diethylamine,

(18) 2,2'-(1-carboxy ethylidene dithio) diethylamine,

(19) 2,2'-(1-phenyl ethylidene dithio) diethylamine,

(20) 2,2'-(2-acetoxy benzylidene dithio) diethylamine, and the saltsthereof.

The cosmetic compositions in accordance with the present inventioncontain at least one active compound of formula I above, or at least oneof their salts, in suspension or in solution in water, an alcohol (suchas ethanol or isopropanol), in a hydroalcoholic solution, in an oil, inan emulsion, or in a gel.

The concentration of the active compound of the present invention isgenerally between 0.1 and 20 percent, and preferably between 1 and 10percent, by weight based on the total weight of said composition.

The capillary compositions of the present invention can contain theactive compounds of formula I, either singly, or as an admixture of twoor more of them, or even in admixture with other compounds which areknown to be useful in combatting the oily and unaesthetic appearance ofthe hair.

The capillary compositions of the present invention can also containother components such as penetrating agents or perfumes, which aregenerally employed in cosmetic compositions.

The cosmetic compositions of the present invention can be provided as adry shampoo in the form of a powder or aerosol, not containing a surfaceactive agent. These compositions can usefully be applied to dry hair. Inthe use of such compositions, the same is applied to dry hair and ispermitted to remain thereon for a sufficient period of time, after whichthe hair is then simply brushed.

The composition of the present invention can also be provided in theform of hair setting lacquers or lotions containing at least one activecompound, as defined above, in combination, in a suitable cosmeticvehicle, with at least one conventional cosmetic resin.

Representative useful cosmetic resins include, for instance,polyvinylpyrrolidone; copolymers of polyvinylpyrrolidone and vinylacetate; copolymers of vinyl acetate and an unsaturated carboxylic acidsuch as crotonic acid; copolymers resulting from the polymerization ofvinyl acetate, crotonic acid and an acrylic or methacrylic ester;copolymers resulting from the copolymerization of vinyl acetate and analkyl vinyl ether; and copolymers resulting from the copolymerization ofvinyl acetate, crotonic acid and a vinyl ester of a long carbon chainacid or even an allyl or methallyl ester of a long carbon chain acid.

The cosmetic resins contained in these hair setting lacquer or lotioncompositions can also be colored polymers, that is, polymers containingin the macromolecular chain thereof dye molecules which impart to thehair a particular coloration or shade.

These hair setting lacquer or lotion compositions can also containdirect dyes so as to produce a desired coloration or shade to the hair.They can also contain components which are conventionally employed incosmetic compositions for fixing the hair in a particular state, such aspenetrating agents, cationic compounds, quaternary ammonium salts,vitamins, proteins, more or less hydrolyzed peptides, cellulose orstarch derivatives, surface active agents, dyes, perfumes and the like.

Useful cosmetic vehicles include those conventionally employed for theproduction of hair setting lacquers and lotions or even hair stylingcompositions.

Thus, these cosmetic compositions can employ as the cosmetic vehicle analcohol or a hydroalcoholic solution and when a cosmetic resin ispresent, they provide a hair setting lotion.

The alcoholic or hydroalcoholic solution of the active compound can alsobe admixed with a suitable amount of liquified propellant gas underpressure and be packaged in an aerosol container to thereby provide ahair setting lacquer.

In these hair setting lotions or lacquers, the concentration of theactive compound is generally between 0.1 and 10 weight percent, but,preferably, between 1 and 3 weight percent, based on the total weight ofsaid composition while the concentration of the resin is between,preferably, 0.1 and 10 weight percent of said total composition.

The cosmetic compositions of the present invention can also be providedin the form of a treating shampoo having the appearance of a liquidwhich can be clear, opaque or pearly, or having the appearance of acream or a gel. These shampoo compositions are also effective insignificantly reducing or eliminating an oily and unaesthetic appearanceof the hair.

These shampoo compositions are essentially characterized by the factthat they contain, in combination, at least one anionic, cationic,nonionic or amphoteric detergent with at least one active compound offormula I.

Representative anionic detergents include, for instance, alkyl sulfates,alkyl ether sulfates, alkyl polyether sulfates, alkyl sulfonates (thealkyl groups having from 8 to 18 carbon atoms), sulfated monoglycerides,sulfoned monoglycerides, sulfated alkanolamides, sulfoned alkanolamides,soaps of fatty acids, monosulfosuccinates of fatty alcohols,condensation products of fatty acids with isethionic acid, condensationproducts of fatty acids with methyl taurine, condensation products offatty acids with sarcosine, condensation products of fatty acids withprotein hydrolyzate.

Representative cationic detergents include, for instance, long chainquaternary ammoniums, esters of fatty acids and amino alcohols andpolyetheramines.

Representative non-ionic detergents include, for instance, esters ofpolyols and sugars, condensation product of ethylene oxide on fattyacids, on fatty alcohols, on long chain alkylphenols, on long chainmercaptans, on long chain amides and polyethers of polyhydroxylatedfatty alcohols.

Representative amphoteric detergents include, for instance, asparagine,condensation products of monochloroacetic acid on imidazolines, alkylamino propionates, betain derivatives or amine oxides.

These shampoo compositions contain generally from 0.1 to 15%, butpreferably, from 1 to 10% by weight of the active compound based on thetotal weight of the composition. They also contain for example from 4 to20%, but preferably, from 5 to 10% by weight of detergents in solutionin an aqueous medium.

The shampoos such as defined above can also contain conventionalcosmetic components such as perfumes and dyes. They can also containthickening agents such as alkanolamides of fatty acids, cationicpolymers such as the copolymers of quaternized vinylpyrrolidone,cationic cellulose polymers, cellulose derivatives such as carboxymethylor hydroxymethyl cellulose, esters of long chain polyols, and naturalgums, whereby the composition can be provided in the form of a cream orgel.

Additionally, these shampoos can be provided in the form of powderswhich can either be applied to wet hair, or can be solubilized in asuitable volume of water before washing the hair.

These shampoo compositions can also include dyes and thus be employed tocolor the hair.

Generally, satisfactory results can be obtained by a weekly applicationof the shampoo, which results in a significant reduction and, in certaincases, essentially complete elimination of the oily appearance of thehair, while at the same time providing normal care of the hair.

The present invention also relates to a composition containing theactive compound, as defined above, together with a suitableskin-compatible cosmetically acceptable vehicle, which composition canbe applied to the skin to improve its appearance.

Such skin-applicable, or topically applicable compositions can beprovided preferably in the form of creams, milks, gels, dermatologicalcakes or aerosol foams. These compositions can also be provided in theform of aqueous or hydroalcoholic lotions. They contain generally from0.1 to 15% by weight, based on the total weight of the composition, ofthe active compound defined above. Preferably from 1 to 5% by weight ofthe the active compound is employed.

The present invention also relates to a new compound having the formula:##STR14## wherein R₁ represents either ##STR15## wherein r' and r" eachindependently represent hydrogen, 2-hydroxyethyl, 2-hydroxy propyl or2,3-dihydroxy propyl,

R₂ represents a member selected from the group consisting of

(i) --CH₃ and R₃ is a hydrogen,

(ii) --CO₂ H

(iii) --C₆ H₅ p-OCH₃,

(iv) --C₆ H₅ and R₃ represents methyl for values (ii)-(iv).

(v) ##STR16## (vi) ##STR17## wherein R₄ represents --CH₂ COOH or--COCH₃, and (vii) ##STR18## wherein R₅ represents --OH, --OCH₃, --OC₄H₉ or --OCH₂ COOH, and

R₃ represents hydrogen or methyl for values (v)-(vii), immediatelyabove,

or R₂ and R₃ taken together, form a divalent radical of the formula--(CH₂)_(m) -- or ##STR19## wherein m is 3-5 inclusive and n is 2-5inclusive, and the salts thereof.

Compounds of formula II, above, wherein R₁ is ##STR20## can be providedin the form of a salt with the aid of a mineral or organic acid.Compounds of formula II, above, wherein R₁ is ##STR21## can be providedin the form of a mono- or di-salt obtained with the aid of a mineral ororganic base.

Representative compounds of formula II include:

α,α'-(piperonylidene dithio) disuccinic acid,

2,2'-(piperonylidene dithio) diethylamine,

2,2'-(2-carboxymethyloxy benzylidene dithio) diethylamine,

α,α'-(vanillylidene dithio) disuccinic acid,

2,2'-(vanillylidene dithio) diethylamine,

α,α'-(veratrylidene dithio) disuccinic acid,

2,2'-(veratrylidene dithio) diethylamine,

α,α'-(4-butoxy-3-methoxy benzylidene dithio) disuccinic acid,

2,2'-(4-butoxy-3-methoxy benzylidene dithio) diethylamine,

α,α'-(4-carboxymethyl-3-methoxy benzylidene dithio) disuccinic acid,

2,2'-(4-carboxymethyloxy-3-methoxy benzylidene dithio) diethylamine,

2,2'-(cyclohexylidene dithio) diethylamine,

2,2'-(1-carboxy ethylidene dithio) diethylamine,

2,2'-(1-phenyl ethylidene dithio) diethylamine,

2,2'-(2-acetoxy benzylidene dithio) dimethylamine, and the salts ofthese said compounds.

The present invention also relates to process for preparing the activecompounds such as defined above.

This process can be represented by the following reaction scheme:##STR22## a carbonyl compound (1) is reacted with at least twoequivalents of a thiod (2).

The reaction preferably is carried out in a solvent medium and in thepresence of an acid catalyst.

The solvent, preferably, is an organic acid (such as formic acid oracetic acid), an alcohol, dioxane or a mixture of these particularsolvents.

The acid catalyst is preferably a strong mineral acid or a Lewis acidsuch as for example zinc chloride or boron trifluoride.

However, when the solvent is an organic acid, (principally, formicacid), the reaction is carried out in the absence of a catalyst.

The reaction temperature is generally between 0° and 100° C. and thereaction time between 1 and 48 hours.

The following non-limiting Examples illustrate the invention.

EXAMPLES OF PREPARATION Example 1 α-α'-(p-methoxybenzylidene dithio)disuccinic acid (Compound 3)

A mixture of 54.4 g (0.4 mole) of anisic aldehyde and 120 g (0.8 mole)of α-mercapto succinic acid in 1 liter of formic acid is stirred for twohours under a nitrogen atmosphere. The reaction mixture is permitted tostand for 24 hours at which time it is then concentrated under reducedpressure. The residue is taken up and crystallized in a mixture of waterand ethanol. After filtering and drying 136 g of white crystals having amelting point of 255° C. are obtained.

Analysis: C₁₆ H₁₈ O₉ S₂ : Calc %: C, 45.93; H, 4.33; S, 15.33. Theory%:C, 45.73; H, 4.34; S, 15.18.

Example 2 2,2'-(2-carboxymethyloxy benzylidene dithio) diethylamine(dihydrochloride) (Compound 8)

For a period of two hours a stream of dry gaseous HCl is bubbled into amixture of 90 g (0.5 mole) of o-formyl phenoxyacetic acid and 115 g (1mole) of β-mercaptoethylamine hydrochloride in 1 liter of acetic acid,previously de-aerated by passage therethrough of nitrogen. The reactionmixture is then heated at 60° C., after which it is permitted to standfor 24 hours at ambient temperature. The resulting crystallized productis filtered off and the filtrate is concentrated to dryness, with theresulting residue being recrystallized in a mixture of ethanol andmethanol. 156 g of white crystals melting at 225° C. are thus recovered.

Analysis: C₁₃ H₂₂ Cl₂ N₂ O₃ S₂ : Calc %: S, 16.47; N, 7.19. Theory %: S,16.24; N, 7.04.

Example 3 α,α'-(veratrylidene dithio) disuccinic acid. (Compound 11)

There is heated in acetic acid (300 ml) for two hours at 65° C., withstirring, a mixture of 16.6 g of veratric aldehyde and 30 g ofα-mercaptosuccinic acid, in the presence of a small amount of borontrifluoride, in the form of an acetic complex. After 12 hours of rest,the reaction mixture is concentrated under reduced pressure and thesolid obtained is crystallized in a mixture of benzene and ethylacetate. After filtering and drying, 31 g of white crystals melting at187° C. are recovered.

Analysis: C₁₇ H₂₀ O₁₀ S₂ : Calc %: C, 45.53; H, 4.50; S, 14.30. Theory%: C, 45.24; H, 4.74; S, 14.38.

Under the same conditions as those described above, the compounds listedin Table I below have been prepared.

                                      TABLE 1                                     __________________________________________________________________________    Initial Reactants        Initial Melting                                                                            Elemental                                                                           Calc %                            Compound  Carbonyl       Temp.                                                                             Yield                                                                             Point                                                                              Analysis                                                                            Theory %                          No.   Thiol                                                                             Compound Solvent                                                                             °C.                                                                        %   °C.                                                                         C  H  N  S                              __________________________________________________________________________    1     a   Acetone  Ethanol                                                                             0° C.                                                                      80  215°                                                                              10.50                                                                            24.00                                                                      10.51                                                                            24.31                          2     a   Glyoxylic acid                                                                         Acetic acid                                                                         20°                                                                        65  180°                                                                              9.89                                                                             22.64                                             + dioxan                 9.68                                                                             22.71                          4     a   Anisaldehyde                                                                           Ethanol                                                                              0°                                                                        70  217°                                                                              8.11                                                                             18.60                                                                      8.12                                                                             18.32                          7     a   Piperonal                                                                              Ethanol                                                                             50°                                                                        80  207°                                                                              7.79                                                                             17.84                                                                      7.61                                                                             17.93                          9     b   Vanillin Acetic acid                                                                         20°                                                                        72  225°                                                                        44.23                                                                            4.18  14.76                                                                44.33                                                                            4.12  14.60                          10    a   Vanillin Ethanol                                                                              0°                                                                        55  194°                                                                              7.75                                                                             17.75                                                                      7.54                                                                             17.79                          12    a   Veratric aldehyde                                                                      Ethanol                                                                             50°                                                                        75  169°                                                                              7.46                                                                             17.08                                                                      7.25                                                                             16.94                          13    b   o-butyl vanillin                                                                       Acetic acid                                                                         60°                                                                        50  188°                                                                        48.96                                                                            5.34  13.07                                                                49.01                                                                            5.42  13.04                          14    a   o-butyl vanillin                                                                       Ethanol                                                                             50°                                                                        65  212°                                                                        46.03                                                                            7.24  15.36                                                                45.71                                                                            7.34  15.49                          15    b   o-carboxymethyl                                                                        Acetic acid                                                                         60°                                                                        45  152°                                                                        43.89                                                                            4.09  13.02                                    vanillin                    43.70                                                                            4.30  13.00                          16    a   o-carboxymethyl                                                                        Acetic acid                                                                         60°                                                                        65  114°                                                                        38.44                                                                            5.91                                                                             6.40                                        vanillin                    38.60                                                                            6.30                                                                             6.55                              17    a   Cyclohexanone                                                                          Ethanol                                                                             50°                                                                        80  207°                                                                              9.11                                                                             20.86                                                                      8.97                                                                             20.85                          18    a   Pyruvic acid                                                                           Acetic acid                                                                         50°                                                                        75  220°                                                                              9.42                                                                             21.57                                                                      9.18                                                                             21.87                          19    a   Acetophenone                                                                           Ethanol                                                                             80°                                                                        50  194°                                                                              8.50                                                                             19.47                                                                      8.33                                                                             19.64                          20    a   o-acetyl salicyl                                                                       Acetic acid                                                                         50°                                                                        85  190°                                                                              7.50                                                                             17.17                                    aldehyde                          7.57                                                                             17.11                          __________________________________________________________________________     a = mercaptoethylamine hydrochloride                                          b = mercaptosuccinic acid                                                

EXAMPLES OF COMPOSITIONS Example A Capillary lotion for oily hair

This capillary lotion is used, after shampooing, on wet hair and beforesetting the hair.

    ______________________________________                                        2,2'-(isopropylidene dithio)                                                  diethylamine dihydrochloride                                                  (Compound No. 1)        1        g                                            Vinylacetate/N-vinylpyrrolidone                                               copolymer               1.5      g                                            Perfume                 0.1      g                                            Ethyl alcohol at 25%, sufficient for                                                                  100      g                                            ______________________________________                                    

Example B Milk for oily skin

    ______________________________________                                        α,α'-(p-methoxybenzylidene dithio)                                disuccinic acid (Compound No. 3)                                                                      2.8      g                                            Triethanolamine, sufficient for                                               pH = 8                                                                        Crosslinked polyacrylic acid, sold                                            under the trade name "CARBOPOL 934"                                                                   0.375    g                                            Isopropyl ester of the fatty acid                                             of lanolin              1        g                                            Lanolin oxyethylenated with 5-20                                              moles of ethylene oxide 2.5      g                                            Cetylstearyl alcohol oxyethylenated                                           with 25 moles of ethylene oxide                                                                       3        g                                            Lauric diethanolamide   2        g                                            Methyl p-hydroxybenzoate                                                                              0.1      g                                            Propyl p-hydroxybenzoate                                                                              0.1      g                                            Water, sufficient for   100      g                                            ______________________________________                                    

Example C Capillary lotion for oily hair

    ______________________________________                                        α,α'-(vanillylidene dithio)                                       disuccinic acid (Compound No. 9)                                                                      0.4      g                                            Potassium hydroxide, sufficient for                                           pH = 4.5                                                                      Calcium pantothenate    0.5      g                                            Perfume                 0.1      g                                            Ethyl alcohol (40%), sufficient for                                                                   100      g                                            ______________________________________                                    

Example D Treating lotion for the skin

    ______________________________________                                        2,2'-(cyclohexylidene dithio)                                                 diethylamine, dihydrochloride                                                 (Compound No. 17)       1.5      g                                            Cetyldimethylbenzyl ammonium chloride                                                                 0.2      g                                            Ethylalcohol            13       ml                                           Polyethylene glycol     10       g                                            Perfume                 0.1      g                                            Soluble dyes            0.1      g                                            Sterile demineralized water,                                                  sufficient for          100      g                                            ______________________________________                                    

Example E Clear liquid shampoo

    ______________________________________                                        2,2'-(piperonylidene dithio)                                                  diethylamine, dihydrochloride                                                 (Compound No. 7)        2        g                                            Lauryl alcohol polyoxyethylenated                                             with 12 moles of ethylene oxide                                                                       13       g                                            Copra diethanolamide    4        g                                            Copolymer of quaternized polyvinyl                                            pyrrolidone, sold under the trade                                             name GAFQUAT 755        0.4      g                                            Perfume                 0.2      g                                            Water, sufficient for   100      g                                            ______________________________________                                    

Example F Cream for oily skin

    ______________________________________                                        2,2'-(2-acetoxy benzylidene dithio)                                           diethylamine, dihydrochloride                                                 (Compound No. 20)       1.5      g                                            Cetylstearyl alcohol    2        g                                            Glycerol monostearate   4        g                                            Cetyl alcohol           4        g                                            Isopropyl palmitate     8        g                                            Stearate polyoxyethylenated with                                              20 moles of ethylene oxide                                                                            6        g                                            Calophyllum oil         1        g                                            Propyl p-hydroxy benzoate                                                                             0.3      g                                            Tetradecyltrimethyl ammonium                                                  bromide                 0.3      g                                            Sterile, demineralized water,                                                 sufficient for          100      g                                            ______________________________________                                    

Example G Shampoo powder

    ______________________________________                                        Potassium salt of α,α'-(4-butoxy-3-                               methoxy benzylidene dithio)                                                   disuccinic acid (Compound No. 13)                                                                     12       g                                            Sodium lauryl sulfate   40       g                                            Condensation products of the fatty                                            acids of copra on sodium                                                      isethionate, sold under the trade                                             name "HOSTAPON K.A."    39       g                                            ______________________________________                                    

Example H Dermatological cake

    ______________________________________                                        Bis-(2-amino ethylthio) acetic acid                                                                   2.5      g                                            Sodium alkane sulfonate, sold under                                           the trade name "IGEPON A"                                                                             80       g                                            Liquid lanolin          12       g                                            Purcellin oil           2        g                                            Chlorhexidine           0.5      g                                            Titanium dioxide        2        g                                            Perfume                 2.5      g                                            ______________________________________                                    

Example I Milk for oily skin

    ______________________________________                                        α,α'-(4-carboxymethyloxy-3-methoxy                                benzylidene dithio) disuccinic                                                acid                    1.6      g                                            Triethanolamine, sufficient for                                               pH = 8                                                                        Crosslinked polyacrylic acid, sold                                            under the trade name "CARBOPOL 934"                                                                   0.375    g                                            Isopropyl ester of the fatty acids                                            of lanolin              1        g                                            Lanolin oxyethylenated with 5-20                                              moles of ethylene oxide 2.5      g                                            Cetylstearyl alcohol oxyethylenated                                           with 25 moles of ethylene oxide                                                                       3        g                                            Lauric diethanolamide   2        g                                            Methyl p-hydroxy benzoate                                                                             0.1      g                                            Propyl p-hydroxy benzoate                                                                             0.1      g                                            Water, sufficient for   100      g                                            ______________________________________                                    

Example J Lotion for daily use for the care of oily hair

    ______________________________________                                        2,2'-(piperonylidene dithio)                                                  diethanolamine, dihydrochloride                                                                       0.4      g                                            Pyridoxine camphosulfonate                                                                            0.3      g                                            Perfume                 0.1      g                                            Dye                     0.1      g                                            Ethyl alcohol/water 50%, sufficient                                           for                     100      g                                            ______________________________________                                    

Example K Pearly liquid shampoo

    ______________________________________                                        α,α'-(4-butoxy-3-methoxy benzylidene                              dithio) disuccinic acid 6        g                                            Potassium hydroxide, sufficient                                               for pH = 7.5                                                                  Sodium lauryl sulfate oxyethylenated                                          with 2.2 moles of ethylene oxide                                                                      9        g                                            Sodium monolauryl sulfosuccinate                                                                      1        g                                            Polyethylene glycol distearate                                                                        2        g                                            Lauric diethanolamide   2        g                                            Perfume                 0.3      g                                            Water, sufficient for   100      g                                            ______________________________________                                    

Example L Cream Shampoo

    ______________________________________                                        2,2'-(isopropylidene dithio)                                                  diethylamine            3.5      g                                            Lactic acid, sufficient for                                                   pH = 6.5                                                                      Sodium lauryl sulfate   12       g                                            Condensation product of copra fatty                                           acids on methyl taurine, sold                                                 under the trade name                                                          "HOSTAPON C.T."         40       g                                            Lauric monoethanolamide 2        g                                            Glycerol monostearate   4        g                                            Perfume                 0.2      g                                            Water, sufficient for   100      g                                            ______________________________________                                    

Example M Cream for oily hair

    ______________________________________                                        α,α'-(vanillylidene dithio)                                       disuccinic acid         1.8      g                                            Triethanolamine, sufficient for                                               pH = 6.5                                                                      Stearate polyoxyethylenated, sold                                             under the trade name "Myr 49"                                                                         3        g                                            Glycerol monostearate   4        g                                            Cetyl alcohol           7        g                                            Vaseline (petrolatum) oil                                                                             8        g                                            Isopropyl myristate     5        g                                            Methyl p-hydroxy benzoate                                                                             0.3      g                                            Crosslinked polyacrylic acid, 1%                                              solution, sold under the trade                                                name "CARBOPOL 941"     40       g                                            Water, sufficient for   100      g                                            ______________________________________                                    

This cream is applied to the scalp after a shampoo. One messages lightlythen leaves to rest about 15 minutes and then one rinses.

Example N Clear liquid shampoo

    ______________________________________                                        α,α'-(4-butoxy-3-methoxy benzylidene                              dithio) disuccinic acid 1.5      g                                            Lauryl alcohol polyglycerolated                                               with 4 moles of glycerol                                                                              15       g                                            Copolymer of quaternized N-vinyl-                                             pyrrolidone, sold under the trade                                             name "GAFQUAT 755"      0.4      g                                            Alkylamine polyethoxylated, sold                                              under the trade name "ETHOMEEN                                                18/15"                  0.8      g                                            Perfume                 0.1      g                                            Water, sufficient for   100      g                                            ______________________________________                                    

Example O Lotion for oily skin

    ______________________________________                                        α-α'-(vanillylidene dithio)                                       disuccinic acid         1.4      g                                            Salicylic acid          0.2      g                                            Di-isobutyl cresoxyethoxyethyl                                                dimethylbenzylammonium chloride                                                                       0.3      g                                            Polyethyleneglycol tertio-dodecyl                                             thioether               0.1      g                                            Hydroxyethyl carboxymethyl 2-alkyl                                            imidazolinium, sold under the                                                 trade name "MIRANOL C 2 M"10                                                                          g                                                     Perfume                 0.8      g                                            Sterile, demineralized water,                                                 sufficient for          100      g                                            ______________________________________                                    

Example P Facial lotion

    ______________________________________                                        α,α'-(p-methoxy benzylidene dithio)                               disuccinic acid           0.8 g                                               Triethanolamine, sufficient for                                               pH = 4.5                                                                      Ethyl alcohol             16 g                                                Methyl p-hydroxybenzoate  0.1 g                                               Propyl p-hydroxybenzoate  0.1 g                                               Perfume                   0.8 g                                               Dye                       0.2 g                                               Water, sufficient for     100 g                                               ______________________________________                                    

Example Q Cream for oily skin

    ______________________________________                                        2,2'-(isopropylidene dithio)                                                  diethyl ammonium dicampho-                                                    sulfonate                 1.2 g                                               Sipol wax (Cire de Sipol) 5 g                                                 Glycerol monostearate     2 g                                                 Hydrogenated polyisobutylene                                                                            3 g                                                 Vaseline (petrolatum) oil 3 g                                                 Cetyl alcohol             1 g                                                 Isopropyl ester of the fatty acids                                            of lanolin                3.5 g                                               Methyl p-hydroxybenzoate  0.3 g                                               Water, sufficient for     100 g                                               ______________________________________                                    

Example R Lotion for oily skin

    ______________________________________                                        α,α'-(4-carboxymethyloxy-3-methoxy                                benzylidene dithio) disuccinic acid                                                                    2 g                                                  Triethanolamine, sufficient for                                               pH = 5                                                                        Ethyldiethylene glycol   10 g                                                 Ethanol                  9 g                                                  Butylhydroxyanisole      0.05 g                                               Butylhydroxytoluene      0.05 g                                               Octyl gallate            0.0125 g                                             Perfume                  0.5 g                                                Water, sufficient for    100 g                                                ______________________________________                                    

What is claimed is:
 1. A cosmetic composition for the treatment of theoily appearance of the hair and skin comprising in combination, in asuitable cosmetic vehicle, (1) an effective amount of at least oneactive compound having the formula ##STR23## wherein R₁ represents##STR24## R₂ represents a member selected from the group consisting of(i) --C₆ H₅ p-OCH₃,(ii) --C₆ H₅ (iii) ##STR25## wherein R₄ represents aradical selected from the group consisting of --CH₂ COOH and --COCH₃,and (iv) ##STR26## wherein R₅ represents a radical selected from thegroup consisting of --OH, --OCH₃, --OC₄ H₉ and --OCH₂ COOH, and R₃represents hydrogen or methyl, or R₂ and R₃ together form a divalentradical of the formula, ##STR27## wherein n is 2-5 inclusive, and (2) aneffective amount of at least one of an anionic, cationic, nonionic oramphoteric detergent.
 2. The cosmetic composition of claim 1 wherein theactive compound is selected from the group consisting of(1)α,α'-(p-methoxy benzylidene dithio) disuccinic acid, (2)α,α'-(benzylidene dithio) disuccinic acid, (3) α,α'-(vanillylidenedithio) disuccinic acid, (4) α,α'-(veratrylidene dithio) disuccinicacid, (5) α,α'-(4-butoxy-3-methoxy benzylidene dithio) disuccinic acid,(6) α,α'-(4-carboxymethyloxy-3-methoxy benzylidene dithio) disuccinicacid,and the salts thereof.
 3. The composition of claim 1 wherein saidactive compound is provided in the form of a mono- or di-salt of amineral or organic base when R₁ is ##STR28##
 4. The composition of claim1 wherein said active compound is present in an amount between 0.1 and20 percent by weight based on the total weight of said composition. 5.The composition of claim 1 wherein said active compound is present in anamount between 1 and 10 percent by weight based on the total weight ofsaid composition.
 6. The composition of claim 1 wherein said detergentis present in an amount of 4 to 20 weight percent thereof.
 7. Thecomposition of claim 1 wherein said detergent is present in an amount of5 to 10 weight percent thereof.
 8. The cosmetic composition of claim 1wherein said active compound is α,α'-(vanillylidene dithio) disuccinicacid.
 9. A process for improving the appearance of oily skin or hair soas to reduce or eliminate said oily appearance comprising applying tosaid oily appearing skin or hair an effective amount of a cosmeticcomposition comprising in combination, in a suitable cosmetic vehicle,an effective amount of at least one active compound having the formula##STR29## wherein R₁ represents ##STR30## R₂ represents a memberselected from the group consisting of (i) --C₆ H₅ p-OCH₃,(ii) --C₆ H₅,(iii) ##STR31## wherein R₄ represents a radical selected from the groupconsisting of --CH₂ COOH and --COCH₃, and (iv) ##STR32## wherein R₅represents a radical selected from the group consisting of --OH, --OCH₃,--OC₄ H₉ and --OCH₂ COOH, and R₃ represents hydrogen or methyl, or R₂and R₃ together form a divalent radical of the formula, ##STR33##wherein n is 2-5 inclusive.
 10. A process for improving the appearanceof oily skin or hair so as to reduce or eliminate said oily appearancecomprising applying to said oily appearing skin or hair an effectiveamount of a cosmetic composition comprising in combination in a suitablecosmetic vehicle an effective amount of α,α'-(vanillylidene dithio)disuccinic acid.